Systems and Methods for the Devolatilization of Thermally Produced Liquids

ABSTRACT

Methods and systems for the devolatilization of thermally produced liquids to raise the flash point are disclosed. Various methods and apparatus can be used to effectively reduce the volatile components, such as wiped film evaporator, falling film evaporator, flash column, packed column, devolatilization vessel or tank.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority from U.S. ProvisionalApplication No. 61/693,156, filed Aug. 24, 2012. The foregoing relatedapplication, in its entirety, is incorporated herein by reference.

The present disclosure relates to U.S. Pat. No. 7,572,365; U.S. Pat. No.7,572,362; U.S. Pat. No. 7,270,743, U.S. Pat. No. 8,105,482, U.S. Pat.No. 8,062,503, U.S. Pat. No. 7,905,990, U.S. Pat. No. 8,097,090, andU.S. Pat. No. 5,792,340. U.S. Pat. No. 7,572,365; U.S. Pat. No.7,572,362; U.S. Pat. No. 7,270,743, U.S. Pat. No. 8,105,482, U.S. Pat.No. 8,062,503, U.S. Pat. No. 7,905,990, U.S. Pat. No. 8,097,090, andU.S. Pat. No. 5,792,340, which are, in their entirety, herebyincorporated herein by reference.

FIELD OF THE INVENTION

The present disclosure generally relates to the devolatilization ofthermally produced liquids to raise the flash point. More specifically,the present disclosure is directed to methods and apparatus toeffectively and selectively reduce volatile components of liquidsproduced from the thermal conversion of biomass and petroleum materials.

BACKGROUND OF THE INVENTION

Biomass has been a primary source of energy over much of human history.During the late 1800's and 1900's the proportion of the world's energysourced from biomass dropped, as the commercial development andutilization of fossil fuels occurred, and markets for coal and petroleumproducts dominated. Nevertheless, some 15% of the world's energycontinues to be sourced from biomass, and in developing countries thecontribution of biomass is much higher at 38%. In addition, there hasbeen a new awareness of the impact of the utilization of fossil fuels onthe environment. In particular, the public is more concerned about andaware of the increase of greenhouse gases resulting from the consumptionof fossil fuels.

Biomass, such as wood, wood residues, and agricultural residues, can beconverted to useful products, e.g., fuels or chemicals, by thermal orcatalytic conversion. An example of thermal conversion is pyrolysiswhere the biomass is converted to a liquid and char, along with agaseous co-product by the action of heat in essentially the absence ofoxygen. In a generic sense, pyrolysis is the conversion of biomass to aliquid and/or char by the action of heat, typically without involvingany direct combustion of the biomass feedstock in the primary conversionunit.

Historically, pyrolysis was a relatively slow process where theresulting liquid product was a viscous tar and “pyroligneous” liquor.Conventional slow pyrolysis has typically taken place at temperaturesbelow 400° C., and over long processing times ranging from severalseconds to minutes or even hours with the primary intent to producemainly charcoal and producing liquids and gases as by-products.

A more modern form of pyrolysis, or rapid thermal conversion, wasdiscovered in the late 1970's when researchers noted that an extremelyhigh yield of a light, pourable liquid was possible from biomass. Infact, liquid yields approaching 80% of the weight of the input of awoody biomass material were possible if conversion was allowed to takeplace over a very short time period, typically less than 5 seconds.

The homogeneous liquid product from this rapid pyrolysis, which has theappearance of a light to medium petroleum fuel oil, can be consideredrenewable oil. Renewable oil is suitable as a fuel for clean, controlledcombustion in boilers, industrial furnaces, and for use in diesel andstationary turbines. This is in stark contrast to slow pyrolysis, whichproduces a thick, low quality, two-phase tar-aqueous mixture in very lowyields.

In practice, the short residence time pyrolysis of biomass causes themajor part of its organic material to be instantaneously transformedinto a vapor phase. This vapor phase contains both non-condensable gases(including methane, hydrogen, carbon monoxide, carbon dioxide andolefins) and condensable vapors. It is the condensable vapors thatconstitute the final liquid product and the yield and value of thismaterial is a strong function of the method and efficiency of thedownstream capture and recovery system.

Several methods and systems can be employed to produce rapid or fastpyrolysis liquids, such as fluid transport reactors, bubbling fluid bedreactors, rotating cones, and auger systems to name a few. Given thefact that there is an ever increasing world mandate for green fuelalternatives, the demand for these thermally produced liquids willincrease. The properties of these liquids will should be examined andpotentially altered for the purpose of achieving appropriatetransportation, environmental, handling and commercial applications. Oneliquid property of prime relevance to liquid transportation andappropriate handling practices is the flash point.

The measure of flash point of a liquid is a common gauge of theflammability and is indicated by the maximum temperature at which amaterial can be stored and handled. If the flash point is too low itcauses the fuel to be subject to flashing and possible ignition. Certainproperties of materials are not generally affected by variations in theflash point, such as auto-ignition temperature, fuel injection andcombustion performance. In many jurisdictions, there is a significantdifference in how materials are treated if the flash point is above orbelow a certain threshold. This threshold is typically in the range of55-62° C. as measured by the Pensky-Martens closed cup flash pointtester (e.g. ASTM D-93).

Liquids produced from the thermal conversion of biomass and othercarbonaceous materials are a complex mixture of many different chemicalcompounds. Each of these compounds has a different flash point, and assuch may influence the flammable classification of the product. Forexample, it is known that fast pyrolysis oils contain acetaldehyde whichhas a flash point of −39° C. A small concentration of this material, aslittle as up to 1 wt %, can have a material impact on the flash pointresult.

If a low flash point is recorded for a sample of pyrolysis liquid, itmay not be truly indicative of the combustibility of the whole product.For example, fast pyrolysis oils typically contain 15-30 wt % waterwhich tends to suppress combustibility without specific measures takento ensure flammability. These measures may include heating, atomization,supply of supporting flame and/or another form of heat source, etc. Assuch, a low flash point measurement may unjustifiably classify theseliquids in regard to flammability since the measurement is onlyreflecting the flash point of a small portion of the total product.

The ability to selectively remove some or all of the volatile componentsfrom thermally converted liquids, including fast pyrolysis oils, can beimportant to the classification of the product so that it is acceptablefor transport and handling in the broadest sense.

SUMMARY OF THE INVENTION

In certain embodiments, the invention relates to a method of increasingthe flash point of a starting liquid by devolatilization of the startingliquid, wherein the starting liquid is produced from thermal conversion,the method comprising: supplying the starting liquid to a firstcomponent; heating the first component to a temperature in the range of20° C. to 200° C.; obtaining a processed liquid product, wherein theprocessed liquid has an increased flash point and a reducedconcentration of volatile components as compared to the starting liquid;and obtaining a volatile components product.

In certain embodiments, the invention relates to a method of increasingthe flash point of a starting liquid by devolatilization of the startingliquid, wherein the starting liquid is produced from thermal conversion,the method comprising: supplying the starting liquid to a firstcomponent comprising a wiped film evaporator; a falling film evaporator;a packed column; a devolatilization tank; an outlet, wherein the outletincludes a carbon filter system; an outlet, wherein the outlet includesa scrubber; an outlet, wherein the outlet includes a filter system; anagitator, wherein the agitator is configured to improve the rate ofdevolatilization; a circulation pump, wherein the circulation pump isconfigured to improve the rate of devolatilization; or an apparatus thatis operated under the influence of a vacuum.

In certain embodiments, the invention relates to a system for thermalconversion comprising: a feed system; a reactor; and a plurality ofcondensing chambers, wherein the temperature of the one or more of theplurality of condensing chambers is adjusted to a temperature greaterthan 30° C., such as a temperature in the range of 30 to 50° C., 30 to60° C., or 40 to 75° C.

In certain embodiments, the invention relates to introducing adevolatilized, processed liquid material into at least a second systemor apparatus for further processing, such as a refinery system; afluidized catalytic cracker (FCC); an FCC refinery system; a coker; acoking unit; a field upgrader unit; a hydrotreater; a hydrotreatmentunit; a hydrocracker; a hydrocracking unit; or a desulfurization unit.In certain embodiments, the invention relates to introducing adevolatilized, processed liquid material via injecting, feeding, orco-feeding, the devolatilized liquid material into the at least a secondsystem or apparatus via a mixing zone, a nozzle, a retro-fitted port, aretro-fitted nozzle, a velocity steam line, or a live-tap.

In certain embodiments, the invention relates to further processing thedevolatilized liquid material by co-injecting a petroleum fractionfeedstock and the devolatilized liquid product into the at least asecond system or apparatus, wherein the co-injecting comprisesco-feeding, independently or separately introducing, injecting, feeding,or co-feeding, the petroleum fraction feedstock and the devolatilizedliquid product.

In certain embodiments, the invention relates to further processing thedevolatilized liquid material by co-injecting a renewable fuel oil andthe devolatilized liquid product into the at least a second system orapparatus, wherein the co-injecting comprises co-feeding, independentlyor separately introducing, injecting, feeding, or co-feeding, therenewable fuel oil and the devolatilized liquid product.

In certain embodiments, the invention relates to a method of processing,comprising introducing a devolatilized liquid material into a fluidizedcatalytic cracker (FCC), wherein the devolatilized liquid material isproduced by thermally converting biomass, petroleum materials, or both,to form a starting liquid; supplying the starting liquid to a firstcomponent; heating the first component to a temperature in the range of20° C. to 200° C.; obtaining a devolatilized liquid material, whereinthe devolatilized liquid material has an elevated flash pointtemperature and a reduced concentration of volatile components relativeto said starting liquid; and obtaining a volatile components product.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are included as part of the presentspecification, illustrate the presently preferred embodiments and,together with the general description given above and the detaileddescription of the preferred embodiments given below, serve to explainand teach the principles of the present disclosure.

FIG. 1 illustrates an exemplary thermal conversion unit to produceprimary liquids for use with the present system, according to oneembodiment.

FIG. 2 illustrates an exemplary wiped film evaporator system for usewith the present system, according to one embodiment.

FIG. 3 illustrates exemplary falling film evaporator system for use withthe present system, according to one embodiment.

FIG. 4 illustrates packed column system that accepts liquid from thethermal conversion unit.

FIG. 5 illustrates a method to devolatilize thermally produced liquid ina containment vessel using a stripper system.

FIG. 6 illustrates an embodiment of the present disclosure utilizing aconditioning system.

It should be noted that the figures are not necessarily drawn to scaleand that elements of similar structures or functions are generallyrepresented by like reference numerals for illustrative purposesthroughout the figures. It also should be noted that the figures areonly intended to facilitate the description of the various embodimentsdescribed herein. The figures do not necessarily describe every aspectof the teachings disclosed herein and do not limit the scope of theclaims.

DETAILED DESCRIPTION

The present disclosure generally relates to the devolatilization ofthermally produced liquids to raise the flash point. More specifically,the present disclosure is directed to methods and apparatus toeffectively and selectively reduce volatile components of liquidsproduced from the thermal conversion of biomass and petroleum materials,resulting in an increase in the flash point.

The measure of flash point of a liquid is a common gauge of theflammability and is indicated by the maximum temperature at which amaterial can be stored and handled. If the flash point is too low itcauses the liquid to be subject to flashing and possible ignition.Certain properties of materials are not generally affected by variationsin the flash point, such as auto-ignition temperature, fuel injectionand combustion performance. In many jurisdictions, there is asignificant difference in how materials are treated if the flash pointis below a certain threshold. This threshold is typically in the rangeof 55-62° C. as measured by the Pensky-Martens closed cup flash pointtester (e.g. ASTM D-93), and as such it is preferable to have the flashpoint greater than 60° C.

Biomass, such as wood, wood residues, and agricultural residues, can beconverted to useful products, e.g., fuels or chemicals, by thermal orcatalytic conversion. An example of thermal conversion is pyrolysiswhere the biomass is converted to a liquid and char, along with agaseous co-product by the action of heat in essentially the absence ofoxygen.

Renewable fuels are fuels produced from renewable resources. Examplesinclude biofuels (e.g. vegetable oil used as fuel), ethanol, methanolfrom biomass, or biodiesel and Hydrogen fuel (when produced withrenewable processes), thermo-chemically produced liquids, andcatalytically converted biomass to liquids.

The present system is directed to methods and apparatus to effectivelyreduce the volatile components from those liquids produced from thethermal conversion of biomass, such as pyrolysis. One such example isrenewable oil that was produced from the rapid thermal conversion ofbiomass under the conditions of 400 to 600° C. at a processing residencetime of less than 10 seconds either with or without the action of acatalyst. An example of a catalyst is ZSM-5 or other FCC catalyst.

The volatile components are typically comprised of low molecular weightaldehydes, ketones, and organic acids.

Various methods and apparatus can be used to effectively reduce thevolatile components, such as wiped film evaporator, falling filmevaporator, flash column, packed column, and devolatilization vessel ortank. Following processing using the disclosed methods and systems, aliquid product is obtained that meets the threshold requirements of aflash point above 55-62° C. as measured by the Pensky-Martens closed cupflash point tester (e.g. ASTM D-93).

The wiped film evaporator has the advantage of good heat and masstransfer, temperature control and short contact times. The liquid thatis to be devolatilized typically enters the top of the unit and fallsdown through a rotating distribution system that will enable an evenlyapplied film of the liquid on the surface of the evaporator. Wiperblades on the rotating system create the thin film and also serve tomove the fluid down the inner walls. The devolatilized vapor that isproduced exits the evaporator and can be either disposed or condensedand collected separately. The devolatilized liquid bottoms product flowsdown the evaporator and through a port where it is immediately cooled ifrequired to ensure minimal deleterious effect to the liquid product.

According to one embodiment, the thermally produced liquid or renewableoil is directed to a wiped film evaporator (an example detailed in FIG.2). The short contact time in the unit and precise control of thesurface temperatures and system pressure enable an appropriatedevolatilization of the liquid while reducing any negative effects tothe liquid product. Under appropriate conditions the volatile componentscan be effectively removed using a wiped film evaporator whileminimizing any deleterious thermal effects to the product liquid whileadditionally raising the flash point temperature above the threshold of55-62° C. Preferably the flash point temperature is raised above 60° C.More preferably the flash point temperature is raised above 62° C.According to one embodiment, the temperature of the wiped filmevaporator is adjusted to obtain a liquid film temperature in a rangeless than 200° C. (e.g., in a range between 20° C. and 200° C.). In apreferred embodiment, the temperature of the wiped film evaporator isadjusted to less than 150° C. (e.g., in a range between 20 and 150° C.),and more preferably in the range less than 100° C. (e.g., in a rangebetween 20 and 100° C.).

According to an alternative embodiment, the thermally produced liquid orrenewable fuel is directed to a wiped film evaporator under theinfluence of a vacuum and the temperature of the wiped film evaporatoris adjusted to a range less than 200° C. (e.g., in a range between 20and 200° C.), and preferably in the range less than 150° C. (e.g., in arange between 20 and 150° C.), and more preferably in the range lessthan 100° C. (e.g., in a range between 20 and 100° C.).

According to one embodiment the wiped film evaporator is operated underthe influence of a vacuum and is adjusted in a range of 10 to 100 mmHgwith a thermally produced liquid temperature of 10 to 50° C.

According to one embodiment the wiped film evaporator is operated underthe influence of a vacuum and is adjusted in a range of 100 to 350 mmHgwith a thermally produced liquid temperature of 10 to 100° C.

According to one embodiment the wiped film evaporator is operated underthe influence of a vacuum and is adjusted in a range of 10 to 750 mmHgwith a thermally produced liquid temperature of 10 to 200° C.

Another evaporator system that could be used to achieve thedevolatilization is employing a falling film evaporator. The liquidwhich is to be devolatilized is introduced through the top of the unitand as a result of gravity, the liquid flows down the unit, preferablyin a continuous film. To increase the surface area, tubes can be usedwith heat applied to the walls of the tubes to initiate and control thedegree of vapor production. Separation of the liquid phase from thevapor phase takes place in the tubes. The amount of vapor produced canpositively influence the liquid film by producing a downward velocitythat further shortens the liquid residence time and thereby reduces thelikelihood of negatively affecting the properties of the product liquid.A vacuum can be applied to the system to enable sufficientdevolatilization while minimizing surface temperatures that couldotherwise negatively affect the liquid. Under appropriate conditions thevolatile components can be effectively removed using a falling filmevaporator while minimizing any deleterious thermal effects to theproduct liquid while additionally raising the flash point temperatureabove the threshold of 55-62° C. Preferably the flash point temperatureis raised above 60° C. More preferably the flash point temperature israised above 62° C.

According to one embodiment, the thermally produced liquid or renewablefuel is directed to a falling film evaporator (an example detailed inFIG. 3) and the temperature is adjusted to a range less than 200° C.(e.g., in a range between 20 and 200° C.), and preferably in the rangeless than 150° C. (e.g., in a range between 20 and 150° C.), and morepreferably in the range less than 100° C. (e.g., in a range between 20and 100° C.).

According to one embodiment, the thermally produced liquid or renewablefuel is directed to a falling film evaporator under the influence of avacuum and the temperature of the falling film evaporator is adjusted toa range less than 200° C. (e.g., in a range between 20 and 200° C.), andpreferably in the range less than 150° C. (e.g., in a range between 20and 150° C.), and more preferably in the range less than 100° C. (e.g.,in a range between 20 and 100° C.).

According to one embodiment the falling film evaporator is operatedunder the influence of a vacuum and is adjusted in a range of 10 to 100mmHg with a thermally produced liquid temperature of 10 to 50° C.

According to one embodiment the falling film evaporator is operatedunder the influence of a vacuum and is adjusted in a range of 100 to 350mmHg with a thermally produced liquid temperature of 10 to 100° C.

According to one embodiment the falling film evaporator is operatedunder the influence of a vacuum and is adjusted in a range of 10 to 750mmHg with a thermally produced liquid temperature of 10 to 200° C.

Another system that could be used to achieve devolatilization of theliquid is a packed column. A packed column utilizes a tube, pipe orvessel that contains some form of packing material which enhances heatand mass transfer. The packing material can be randomly placed, orstructured packing. The column can be run under the influence of avacuum. Under appropriate conditions the volatile components can beeffectively removed using a packed column while minimizing anydeleterious thermal effects to the product liquid while additionallyraising the flash point temperature above the threshold of 55-62° C.Preferably the flash point temperature is raised above 60° C. Morepreferably the flash point temperature is raised above 62° C.

According to one embodiment, the thermally produced liquid or renewablefuel is directed to a packed column (an example is detailed in FIG. 4)under the influence of a vacuum and the temperature of the packed columnis adjusted to a range less than 200° C. (e.g., in a range between 20and 200° C.), and preferably in the range less than 150° C. (e.g., in arange between 20 and 150° C.), and more preferably in the range lessthan 100° C. (e.g., in a range between 20 and 100° C.).

According to one embodiment the packed column is operated under theinfluence of a vacuum and is adjusted in a range of 10 to 100 mmHg witha thermally produced liquid temperature of 10 to 50° C.

According to one embodiment the packed column is operated under theinfluence of a vacuum and is adjusted in a range of 100 to 350 mmHg witha thermally produced liquid temperature of 10 to 100° C.

According to one embodiment the packed column is operated under theinfluence of a vacuum and is adjusted in a range of 10 to 750 mmHg witha thermally produced liquid temperature of 10 to 200° C.

The thermally produced liquid is circulated through the packed columnfor duration of time such that the flash point temperature of the liquidis raised above about 55 to 62° C. Preferably the flash pointtemperature is raised above 60° C. More preferably the flash pointtemperature is raised above 62° C.

According to one embodiment, the thermally produced liquid or renewablefuel is directed to a devolatilization tank or vessel under theinfluence of a vacuum and the temperature of the devolatilization tankor vessel is adjusted to a range less than 200° C. (e.g., in a rangebetween 20 and 200° C.), and preferably in the range less than 150° C.(e.g., in a range between 20 and 150° C.), and more preferably in therange less than 100° C. (e.g., in a range between 20 and 100° C.).

According to one embodiment, the thermally produced liquid or renewablefuel is directed to a devolatilization tank or vessel under theinfluence of positive headspace ventilation and the temperature of thedevolatilization tank or vessel is adjusted to a range less than 200° C.(e.g., in a range between 20 and 200° C.), and preferably in the rangeless than 150° C. (e.g., in a range between 20 and 150° C.), and morepreferably in the range less than 100° C. (e.g., in a range between 20and 100° C.).

According to one embodiment the devolatilization tank or vessel isoperated under the influence of a vacuum and is adjusted in a range of10 to 100 mmHg with a thermally produced liquid temperature of 10 to 50°C. The temperature may be controlled (heated or cooled) through the useof a heat exchanger in the circulation loop and/or a jacket and/or coilin the tank.

According to one embodiment the devolatilization tank or vessel isoperated under the influence of a vacuum and is adjusted in a range of100 to 350 mmHg with a thermally produced liquid temperature of 10 to100° C. The temperature may be controlled (heated or cooled) through theuse of a heat exchanger in the circulation loop and/or a jacket and/orcoil in the tank.

According to one embodiment the devolatilization tank or vessel isoperated under the influence of a vacuum and is adjusted in a range of10 to 750 mmHg with a thermally produced liquid temperature of 10 to200° C. The temperature may be controlled (heated or cooled) through theuse of a heat exchanger in the circulation loop and/or a jacket and/orcoil in the tank.

According to one embodiment the devolatilization tank or vessel ismaintained at 10 to 100° C. while having a flow of air or other gas(e.g., nitrogen, synthesis gas, thermally produced by-product gas, etc.)in the head space of the tank above the liquid. The flow of gas isadjusted to allow 0.01 to 2 volume changes per hour and more preferably1 to 5 volume changes per hour. The temperature may be controlled(heated or cooled) through the use of a heat exchanger in thecirculation loop and/or a jacket and/or coil in the tank.

The thermally produced liquid is retained in the devolatilization tankor vessel for duration of time such that the flash point temperature ofthe liquid is raised above about 55 to 62° C. Preferably the flash pointtemperature is raised above 60° C. More preferably the flash pointtemperature is raised above 62° C.

According to one embodiment, the volatile components evolved from thevessel are directed to a flare.

In a further embodiment, the tank or vessel is coupled with an activatedcarbon filter system on the vent. The activated carbon filter systemserves to capture volatile components that are evolved from the tank orvessel during the devolatilization procedure. In an alternativeembodiment, the tank or vessel is coupled with a scrubber or filtersystem on the outlet. The scrubber or filter system serves to capturevolatile components that are evolved from the tank or vessel during thedevolatilization procedure.

Various methods can also be employed to increase the rate ofdevolatilization. According to one embodiment, a stripper gas can beused as a method to create bubbling action in the tank or vessel andserve to increase the surface area of contact thereby improving the rateof devolatilization. The stripper gas may be a product gas from thethermal conversion unit, nitrogen, air, or an inert gas. In analternative or further embodiment, the tank or vessel is equipped withan agitator and/or circulation pump to actively increase the surfacearea of contact thereby improving the rate of devolatilization.

Suitable liquids prepared from thermal conversion of biomass orpetroleum materials may be treated with one or more devolatilitizationprocesses to reduce the amount or concentration of one or more volatilecomponents, wherein the resulting liquid product has an elevated flashpoint, relative to the flash point of the thermally converted liquidprior to devolatilization, for example, the resulting liquid product mayhave a flash point that is elevated by at least 1° C., relative to theflash point of the thermally converted liquid prior to devolatilization,such as elevated by at least 2° C.; at least 3° C.; at least 4° C.; atleast 5° C.; at least 6° C.; at least 7° C.; at least 8° C.; at least 9°C.; at least 10° C.; at least 15° C.; at least 20° C.; at least 25° C.;or elevated by at least 30° C.

In certain embodiments, suitable liquids prepared from thermalconversion of biomass or petroleum materials may be treated with one ormore devolatilitization processes to reduce the amount or concentrationof one or more volatile components, wherein the resulting liquid producthas a flash point that is elevated in the range of between 1° C. to 50°C., relative to the flash point of the thermally converted liquid priorto devolatilization, for example, the resulting liquid product has aflash point that is elevated in the range of between 1° C. to 5° C.,such as elevated in the range of between 2° C. to 7° C.; between 3° C.to 9° C.; between 4° C. to 10° C.; between 5° C. to 15° C.; between 10°C. to 15° C.; between 10° C. to 20° C.; between 15° C. to 25° C.; orelevated in the range of between 20° C. to 30° C.

Suitable liquids prepared from thermal conversion of biomass orpetroleum materials may be treated with one or more devolatilitizationprocesses to reduce the amount or concentration of one or more volatilecomponents, wherein the resulting liquid product has an elevated flashpoint, relative to the flash point of the thermally converted liquidprior to devolatilization. For example, the suitable liquids to undergoa devolatilization process may be reiteratively treated by the sameprocess one or more times, such as 2-3, 3-5, or 4-6 times by the sameprocess to produces a resulting liquid product that has an elevatedflash point, relative to the flash point of the thermally convertedliquid prior to devolatilization. Alternatively, the suitable liquids toundergo a devolatilization process may be treated by a combination ofone or more of the following systems (or component of a system),comprising: a wiped film evaporator; a falling film evaporator; a packedcolumn; a devolatilization tank; an outlet system comprising a filtersystem, such as a carbon filter system; an outlet system comprising ascrubber system; an agitator system; a circulation pump; a systemoperated under vacuum, for example, under a vacuum in the range ofbetween 10 to 750 mmHg, such as between 10 to 600 mmHg, between 10 to500 mmHg, between 10 to 400 mmHg, between 10 to 300 mmHg, between 10 to200 mmHg, between 10 to 100 mmHg, between 10 to 50 mmHg, between 10 to25 mmHg, between 25 to 75 mmHg, between 50 to 100 mmHg, between 100 to750 mmHg, between 100 to 500 mmHg, between 100 to 400 mmHg, between 100to 350 mmHg, between 100 to 300 mmHg, or between 100 to 200 mmHg.

In certain embodiments, suitable liquids prepared from thermalconversion of biomass or petroleum materials (“pre-devolitizationliquids”) may have a flash point temperature in the range of between 30°C. to 60° C., such as a flash point temperature in the range of between30° C. to 58° C.; between 30° C. to 55° C.; between 30° C. to 50° C.;between 30° C. to 45° C.; between 30° C. to 40° C.; between 35° C. to60° C.; between 35° C. to 57° C.; between 35° C. to 55° C.; between 35°C. to 50° C.; between 35° C. to 45° C.; between 40° C. to 60° C.;between 40° C. to 58° C.; between 40° C. to 55° C.; between 40° C. to50° C.; between 40° C. to 45° C.; between 50° C. to 60° C.; between 50°C. to 58° C.; between 50° C. to 55° C.; or a flash point temperature inthe range of between 52° C. to 58° C.

In certain embodiments, a pre-devolitization liquid may be treated withone or more devolatilitization processes and the resulting liquidproduct may have a flash point temperature in the range of between 40°C. to 90° C., such as a flash point temperature in the range of between40° C. to 85° C.; between 40° C. to 80° C.; between 40° C. to 75° C.;between 40° C. to 70° C.; between 40° C. to 65° C.; between 40° C. to60° C.; between 50° C. to 90° C.; between 50° C. to 80° C.; between 50°C. to 70° C.; between 50° C. to 60° C.; between 55° C. to 90° C.;between 55° C. to 85° C.; between 55° C. to 80° C.; between 55° C. to75° C.; between 55° C. to 70° C.; between 60° C. to 90° C.; between 60°C. to 85° C.; between 60° C. to 80° C.; between 60° C. to 70° C.;between 65° C. to 90° C.; between 65° C. to 80° C.; between 70° C. to90° C.; between 70° C. to 85° C.; or a flash point temperature in therange of between 70° C. to 80° C.

The operating conditions of the thermal conversion system can beadjusted to allow in-situ removal of the volatile components. FIG. 1 anexample of a thermal conversion system 100. The downstream system iscomprised of several unit operations. The system shown in FIG. 1comprises a feed system 105 for supplying the selected feedstock, areactor 110, a first condensing column 120, and a second condensingcolumn 130. By adjusting the temperature of the first column, volatilecomponents of the produced liquid can be caused to go further downstreamto the second column. The liquid remaining in the first column will havea flash point that is above the threshold point of 55-62° C.

According to one embodiment, the first condensing column of a thermalconversion system is operated to cause the temperature in the column tobe greater than 30° C. In a further embodiment, the first condensingcolumn of the thermal conversion system is operated to cause thetemperature in the column to be in a temperature range of 30° C. to 60°C. In other embodiments, the first condensing column of a thermalconversion system is operated to cause the temperature in the column tobe in a temperature range of 30° C. to 50° C. or in the range of 40° C.to 75° C. According to this embodiment it can be practiced independentto the methods as described above or as a pretreatment method in advanceof the methods as described above.

According to one embodiment, the second condensing column of a thermalconversion system is operated to cause the temperature in the column tobe at a temperature of greater than 30° C. More preferably, the secondcondensing column of a thermal conversion system is operated to causethe temperature in the column to be in a temperature range of 30° C. to60° C., or 30° C. to 50° C., or 40° C. to 75° C.

FIG. 6 illustrates an example of integrating the downstream of a thermalconversion unit with a system to devolatilize the thermally producedliquid and produce a product that meets the flash point threshold. Thedevolatilization system can be a wiped film evaporator, falling filmevaporator, packed column, devolatilization vessel or tank, or otherevaporation system.

According to one embodiment, all of the liquid from the downstreamliquid collection system of the thermal conversion unit is directed to adevolatilization system. Alternatively, only the first column liquidfrom the downstream liquid collection system of the thermal conversionunit is directed to a devolatilization system. In a further alternative,only the second column liquid from the downstream liquid collectionsystem of the thermal conversion unit is directed to a devolatilizationsystem.

FIG. 6 illustrates an example of integrating the downstream of a thermalconversion unit with a liquid conditioning system then directing theconditioned liquid to a devolatilization unit whereby the conditionedand devolatilized thermally produced liquid meets the flash pointthreshold. The conditioning system can be a screen, filter, centrifuge,decanter, or other such separation system. The devolatilization systemcan be a wiped film evaporator, falling film evaporator, packed column,devolatilization vessel or tank, or other evaporation system.

According to one embodiment, all of the liquid from the downstreamliquid collection system of the thermal conversion unit is directed to aconditioning system and the conditioned liquid product is then directedto a devolatilization system whereby the resultant liquid product meetsthe flash point threshold.

The systems and methods as described above can also serve to reduce thewater content of thermally produced liquid. Along with a controlledamount of devolatilized organic chemicals, water can also be removed byoperating the above systems under the more severe conditions of deepervacuum or slightly higher operating temperature.

Fluid catalytic cracking (FCC) is a conversion process used in petroleumrefineries, and is widely used to convert the high-boiling,high-molecular weight hydrocarbon fractions of petroleum crude oils tomore valuable gasoline, olefinic gases, and other products. For example,catalytic cracking produces more gasoline with a higher octane rating,and also produces byproduct gases that are more olefinic, and hence morevaluable, than those produced by thermal cracking.

The feedstock to an FCC is usually that portion of the crude oil thathas an initial boiling point of 340° C. or higher at atmosphericpressure and an average molecular weight ranging from about 200 to 600or higher. This portion of crude oil is often referred to as heavy gasoil. The FCC process vaporizes and breaks the long-chain molecules ofthe high-boiling hydrocarbon liquids into much shorter molecules bycontacting the feedstock, at high temperature and moderate pressure,with a fluidized powdered catalyst.

In certain embodiments, the liquid product that results from thedevolatization processes discussed herein, may be introduced intoanother system or apparatus for further processing. For example, incertain embodiments, the liquid product that results from thedevolatization processes discussed herein, may be introduced into arefinery system, such as a fluidized catalytic cracker (FCC), a FCCrefinery system, a coker, a coking unit, a field upgrader unit, ahydrotreater, a hydrotreatment unit, a hydrocracker, a hydrocrackingunit, or a desulfurization unit. For example, the system or apparatus isor comprises a FCC refinery system; the system or apparatus is orcomprises a coker; the system or apparatus is or comprises ahydrotreater; or the system or apparatus is or comprises a hydrocracker.In certain embodiments, the system or apparatus employed to furtherprocess the devolatilized liquid may include a retro-fitted refinerysystem.

In certain embodiments, the liquid product that results from thedevolatization processes discussed herein, may be further processed by amethod that includes introducing, injecting, feeding, or co-feeding, thedevolatilized liquid product into a refinery system via a mixing zone, anozzle, a retro-fitted port, a retro-fitted nozzle, a velocity steamline, or a live-tap. For example, the method may comprise processing apetroleum fraction feedstock with the devolatilized liquid product, ormay comprise processing a renewable fuel oil with the devolatilizedliquid product.

In certain embodiments, the processing may comprise co-injecting thepetroleum fraction feedstock and the devolatilized liquid product, suchas co-feeding, independently or separately introducing, injecting,feeding, or co-feeding, the petroleum fraction feedstock and thedevolatilized liquid product into a refinery system. For example, thepetroleum fraction feedstock and the devolatilized liquid product may beprovided, introduced, injected, fed, or co-fed proximate to each otherinto the reactor, reaction zone, reaction riser of the refinery system.In certain embodiments, the devolatilized liquid product is provided,introduced, injected, fed, co-fed into the reactor, reaction zone, orreaction riser of the refinery system proximate, upstream, or downstreamto the delivery or injection point of the petroleum fraction feedstock.In certain embodiments, the petroleum fraction feedstock and thedevolatilized liquid product come in contact with each other uponintroduction, delivery, injection, feeding, co-feeding into the refinerysystem, into the reactor, into the reaction zone, or into the reactionriser. In certain embodiments, the petroleum fraction feedstock and thedevolatilized liquid product come in contact with each other subsequentto entering the refinery system, the reactor, the reaction zone, or thereaction riser. In certain embodiments, the petroleum fraction feedstockand the devolatilized liquid product make first contact with each othersubsequent to entering into, introduction into, injection into, feedinginto, or co-feeding into the refinery system, the reactor, the reactionzone, or the reaction riser. In certain embodiments, the petroleumfraction feedstock and the devolatilized liquid product are co-blendedprior to injection into the refinery system.

In certain embodiments, the processing may comprise co-injecting therenewable fuel oil and the devolatilized liquid product, such asco-feeding, independently or separately introducing, injecting, feeding,or co-feeding, the renewable fuel oil and the devolatilized liquidproduct into a refinery system. For example, the renewable fuel oil andthe devolatilized liquid product may be provided, introduced, injected,fed, or co-fed proximate to each other into the reactor, reaction zone,reaction riser of the refinery system. In certain embodiments, thedevolatilized liquid product is provided, introduced, injected, fed,co-fed into the reactor, reaction zone, or reaction riser of therefinery system proximate, upstream, or downstream to the delivery orinjection point of the renewable fuel oil. In certain embodiments, therenewable fuel oil and the devolatilized liquid product come in contactwith each other upon introduction, delivery, injection, feeding,co-feeding into the refinery system, into the reactor, into the reactionzone, or into the reaction riser. In certain embodiments, the renewablefuel oil and the devolatilized liquid product come in contact with eachother subsequent to entering the refinery system, the reactor, thereaction zone, or the reaction riser. In certain embodiments, therenewable fuel oil and the devolatilized liquid product make firstcontact with each other subsequent to entering into, introduction into,injection into, feeding into, or co-feeding into the refinery system,the reactor, the reaction zone, or the reaction riser. In certainembodiments, the renewable fuel oil and the devolatilized liquid productare co-blended prior to injection into the refinery system.

In one exemplary embodiment of the present disclosure, a thermallyproduced liquid from the conversion of a wood based feedstock had aninitial flash point of 55.5° C. The requirement threshold for theapplication was greater than 60° C. Using a ventilated tank withcontinuous agitation the liquid was devolatilized to the point where aflash point of 64.7° C. was achieved:

Sample Date: Flash Point (° C.) Day 1 55.5 Day 4 61.6 Day 7 64.5 Day 1464.7

In the description above, for purposes of explanation only, specificnomenclature is set forth to provide a thorough understanding of thepresent disclosure. However, it will be apparent to one skilled in theart that these specific details are not required to practice theteachings of the present disclosure.

Moreover, the various features of the representative examples and thedependent claims may be combined in ways that are not specifically andexplicitly enumerated in order to provide additional useful embodimentsof the present teachings. It is also expressly noted that all valueranges or indications of groups of entities disclose every possibleintermediate value or intermediate entity for the purpose of originaldisclosure, as well as for the purpose of restricting the claimedsubject matter. It is also expressly noted that the dimensions and theshapes of the components shown in the figures are designed to help tounderstand how the present teachings are practiced, but not intended tolimit the dimensions and the shapes shown in the examples.

Systems and methods for the devolatilization of thermally producedliquids to raise the flash point have been disclosed. It is understoodthat the embodiments described herein are for the purpose of elucidationand should not be considered limiting the subject matter of thedisclosure. Various modifications, uses, substitutions, combinations,improvements, methods of productions without departing from the scope orspirit of the present invention would be evident to a person skilled inthe art.

What is claimed is:
 1. A method of increasing the flash point of astarting liquid by devolatilization of the starting liquid, wherein thestarting liquid is produced from thermal conversion, the methodcomprising: i) supplying the starting liquid to a first component; ii)heating the first component to a temperature in the range of 20° C. to200° C.; iii) obtaining a processed liquid product, wherein theprocessed liquid has an increased flash point and a reducedconcentration of volatile components as compared to the starting liquid;and iv) obtaining a volatile components product.
 2. The method of claim1, wherein the first component is a wiped film evaporator.
 3. The methodof claim 1, wherein the first component is a falling film evaporator. 4.The method of claim 1, wherein the first component is a packed column.5. The method of claim 1, wherein the first component is adevolatilization tank.
 6. The method of claim 1, wherein the firstcomponent comprises an outlet, wherein the outlet includes a carbonfilter system.
 7. The method of claim 1, wherein the first componentcomprises an outlet, wherein the outlet includes a scrubber.
 8. Themethod of claim 1, wherein the first component comprises an outlet,wherein the outlet includes a filter system.
 9. The method of claim 1,wherein heating comprises heating the first component to a temperaturein the range of 20° C. to 150° C.
 10. The method of claim 1, whereinheating comprises heating the first component to a temperature in therange of 20° C. to 100° C.
 11. The method of claim 1, wherein thevolatile components product is directed to a flare.
 12. The method ofclaim 1, further comprising introducing a stripper gas into the firstcomponent.
 13. The method of claim 12, wherein the stripper gascomprises one or more of nitrogen, air, inert gas, and the product gasobtained during the thermal conversion process.
 14. The method of claim1, wherein the first component comprises an agitator, wherein theagitator is configured to improve the rate of devolatilization.
 15. Themethod of claim 1, wherein the first component comprises a circulationpump, wherein the circulation pump is configured to improve the rate ofdevolatilization.
 16. The method of claim 1, wherein the first componentis operated under the influence of a vacuum.
 17. The method of claim 16,wherein the first component is adjusted in a range of 10 to 100 mmHgwith a product temperature of 10 to 50° C.
 18. The method of claim 16,wherein the first component is adjusted in a range of 100 to 350 mmHgwith a product temperature of 10 to 100° C.
 19. The method of claim 16,wherein the first component is adjusted in a range of 10 to 750 mmHgwith a product temperature of 10 to 200° C.
 20. A system for thermalconversion comprising: i) a feed system; ii) a reactor; and iii) aplurality of condensing chambers, wherein the temperature of the one ormore of the plurality of condensing chambers is adjusted to atemperature greater than 30° C.
 21. The system of claim 20, wherein thetemperature of the one or more of the plurality of condensing chambersis adjusted to a temperature in the range of 30 to 50° C.
 22. The systemof claim 20, wherein the temperature of the one or more of the pluralityof condensing chambers is adjusted to a temperature in the range of 30to 60° C.
 23. The system of claim 20, wherein the temperature of the oneor more of the plurality of condensing chambers is adjusted to atemperature in the range of 40 to 75° C.
 24. The method of claim 1,wherein the flash point of the devolatilized, processed liquid iselevated in the range of between 1° C. to 50° C., relative to the flashpoint of the thermally converted starting liquid prior todevolatilization.
 25. The method of claim 1, wherein the flash point ofthe devolatilized, processed liquid is elevated by at least 5° C.,relative to the flash point of the thermally converted starting liquidprior to devolatilization.
 26. The method of claim 1, wherein the flashpoint of the thermally converted starting liquid prior todevolatilization comprises a flash point temperature in the range ofbetween 30° C. to 60° C.
 27. The method of claim 26, wherein the flashpoint of the devolatilized, processed liquid comprises a flash pointtemperature in the range of between 40° C. to 90° C.
 28. The method ofclaim 1, wherein the resulting devolatilized, processed liquid isintroduced into at least a second system or apparatus for furtherprocessing.
 29. The method of claim 28, wherein the at least a secondsystem or apparatus for further processing comprises: a refinery system;a fluidized catalytic cracker (FCC); an FCC refinery system; a coker; acoking unit; a field upgrader unit; a hydrotreater; a hydrotreatmentunit; a hydrocracker; a hydrocracking unit; or a desulfurization unit.30. The method of claim 29, wherein the at least a second system orapparatus for further processing comprises a fluidized catalytic cracker(FCC).
 31. The method of claim 28, wherein the introduction of theresulting devolatilized, processed liquid comprises: injecting, feeding,or co-feeding, the devolatilized liquid product into the at least asecond system or apparatus via a mixing zone, a nozzle, a retro-fittedport, a retro-fitted nozzle, a velocity steam line, or a live-tap. 32.The method of claim 31, wherein the further processing comprisesco-injecting a petroleum fraction feedstock and the devolatilized liquidproduct into the at least a second system or apparatus; wherein theco-injecting comprises co-feeding, independently or separatelyintroducing, injecting, feeding, or co-feeding, the petroleum fractionfeedstock and the devolatilized liquid product.
 33. The method of claim31, wherein the further processing comprises co-injecting a renewablefuel oil and the devolatilized liquid product into the at least a secondsystem or apparatus; wherein the co-injecting comprises co-feeding,independently or separately introducing, injecting, feeding, orco-feeding, the petroleum fraction feedstock and the devolatilizedliquid product.
 34. A method of processing, comprising introducing adevolatilized liquid material into a fluidized catalytic cracker (FCC),wherein the devolatilized liquid material is produced by: i) thermallyconverting biomass, petroleum materials, or both, to form a startingliquid; ii) supplying the starting liquid to a first component; iii)heating the first component to a temperature in the range of 20° C. to200° C.; iv) obtaining a devolatilized liquid material, wherein thedevolatilized liquid material has an elevated flash point temperatureand a reduced concentration of volatile components relative to saidstarting liquid; and v) obtaining a volatile components product.